Cyanoalkyl-nitrophenyl carbonates

ABSTRACT

COMPOUNDS OF STRUCTURE   (2,4-DI(O2N-),6-R1-PHENYL)-OOC-O-R2   WHERE R1 IS ALKYL OF ONE TO TEN CARBON ATOMS, AND R2 IS CYANOALKYL CONTAINING FROM ONE TO FOUR CARBON ATOMS IN THE ALKYL GROUP. THESE COMPOUNDS ARE EXTREMELY EFFECTIVE AS ACARICIDES AND ALSO HAVE FUNGICIDAL AND HERBICIDAL ACTIVITY.

Un ted States Patent '7 Claims ABSTRACT OF THE DISCLOSURE Compounds of structure where R is alkyl of one to ten carbon atoms, and R is cyanoalkyl oontainingfrom' one to four carbon atoms in the alkyl group. These compounds'are extremely eifective as acaricides and also have fungicidal and herbicidal activity.

Nitrophenyl carbonates devoid of cyano substituents are known and have pesticidal activity. For example, US.

3,287,611 discloses compounds of structure where R is lower alkyl and these compounds have acaricidal activity. Likewise, US. 3,234,260 discloses similar acaricidal compounds which are further substituted in the phenyl ring. U .8. 3,198,824 discloses as fungicides and herbicides compounds of structure where R is alkyl and Ar is aryl.

It has now been found, however, that surprisingly superior acaricides, herbicides and fungicides are obtained by providing compounds of structure where R is an alkyl group of one to ten carbon atoms and R is a cy'anoalkyl group containing from one to four carbon atomsin its alkyl position.

The compounds of the invention can be prepared by phosgenation of. the compound NC -R --0H giving NC-R O'CO--Cl and then reacting this compound with a dinitro-alkylphenol. The same type of compounds can be obtained by reaction of the appropriate chloroformic acid with the appropriate phenolate.

Preparation of the compounds is illustrated as follows:

In a reaction flask, equipped with a stirrer, a thermometer, a dropping funnel and a gas inlet tube; 96 grams of acetone cyanohydrin, '(CH C(OH)CN, was mixed with 300 ml. of toluene. During one hour, 113 grams of phosgene was introduced at a temperature of 5 to 0 C. Subsequently, 89.5 grams of pyridine was added in 1.5 hours at a temperature of 0 to 5 C. The hydrochloric acid salt of pyridine precipitated. Stirring was continued 7 3,594,400 Patenteduly 20, 1 971 at a temperature of 0 C. for another hour, whereafterair was passed through in order to remove traces of phosgene.

Then 270 grams of 95% 2.4-dinitro-6-sec. butylphenol dissolved in ml. of toluene was added. 89.5 grams of pyridine was added dropwise-ata-temperature of 5 to 10 C. The mixture .was filtered and the residue washed with toluene. The toluene solution was extracted with water. and dried above sodium sulphate.

After removing the sodium sulphate the toluene was vaporized underdiminished pressure. The oil so obtained was crystallized from toluene. In this way 157 grams of very light colored crystalline product was obtained which melted at 87 C. In this compound R was sec.-butyl and R2 Was In the same way the following compounds of the invention were prepared:

Product R1 R2 pOlii i f ,CN Methyl lCH; 108

Sec. butyl CHgQN 76;

H D0 -CH3 74 Do CH2CHZCN 66 CN D0 (|:-CH3 87 Sec amyl CH2CN 64 H D0 JCH] Oil Do 'CH.H."CN 85 CN 1 30 J-CHQ CN S... Wig.-. 5H. ou

form pesticidal preparations by mixing them with solid ,1

diluents and if desired with dispersing agents, emulsifying agents or emulsifiable solutions. Generally the wettable powders contain 50-90 weight percent of the active compound and for the rest a dispersing agent, a wetting agent, and a carrier. If the active compound is a liquid or oil, the content of active compound is below 50 weight percent. The liquid compounds are then adsorbed on adsorbing carriers. Emulsifiable solutions can be obtained by the solution of the active compound in a solvent or mixture of solvents. Suitable solvents are alcohols, ketones, ethers, aromatic hydrocarbons and petroleum fractions.- As indicated, dispersing agents, wetting agents, or emulr sifying agents can be added. 0

EVALUATION OR- COMPOUNDS Example I In a test for determining herbicidal residual action, the active compound was sprayed at concentrations of 4, 2, 1, 1.5, and 0.25 kg. of active compound per hectare on soil rich in weeds. All compounds were formulated in the same way. The following results expressed as LD in kg. active compound per hectare are obtained.

The numbers in Table III represent the percentage of dead mites.

TABLE I TABLE III Compounded coded R1 R2 LDm 5 Dead mites A.-- Sec.buty1 CH 0.75 Com ound 200 m 40 .m. 8 .m A; do -oHioN 0. as p pp pp pp 100 as 07 B- See. butyl CH2-CH: 0.65 100 83 23 100 100 100 B1 .-do ON 0.60 100 8 l F1"?: 100 06 -CCH9 2.4-d1n1tro-G-see. butyl-phenolester of {iB-dimethylaeryllc H acid 100 80 27 C Sec. butyl III 5. 40 l A commercial aeariclde known as Aerieid.

-CCHa It is quite clear from the results shown in Table HI that (3H3 10 the compounds of the invention are excellent acaricides.

The compounds of the invention appear to be partic- Cl ularly suitable for a combined acaricidal and fungicidal -0-CH5 action and preferred species of useful compounds are (3H3 those identified above as C and F It will be understood that numerous changes and variajggz 83% tions may be made without departing from the spirit and s 1 OH CH 1 2O scope of the invention. ec.amy za E, d0 -oH1-oH2oN 0.80 We Glam- 1. A compound of structure F Sec.amyl H 5.00

on, Nozoc-om F do ON 0. 75

a where R is an alkyl group of one to ten carbon atoms H3 and R is a cyanoalkyl group containing from one to four carbon atoms in the alkyl group. Example H 2. A compound as in claim 1 where R is a secondary TABLE II Percent of glierkin surface covered with mildew after treatment Compound 80 p.p.m. 40 p.p.m. 20 p.p.m. 10 p.p.m.

R1=sec. oetyl CN l i 7 10.8 24.3 57.3 R =t|3CH The excellent fungicidal activity of the compounds, particularly cyanoisopropyl-2.4-dinitro-6-sec. amylphenylcarbonate (F is clearly shown.

Example III The examination of the acaricidal action was carried out on mites of the genus -Bryodia on leaves of the brown bean. Leaves were sprayed in petri dishes with aqueous formulations of the active compounds in concentrations of 200, 40, and 8 p.p.m. in a quantity corresponding to 1,000 liters per hectare. Before the leaves were sprayed 25 living mites were present on each leaf. Tests were carried out in quadruple.; after 1 and 2 days the dead mites were counted.

butyl group and R is ON CH.

3. A compound as in claim 1 where R is secondary amyl and R is (3N -CC1I3 C113 4. A compound as in claim 1 where R is a secondary butyl group and R is CH CN.

5. A compound as in claim 1 where R is a secondary butyl group and R is (IDN CHOHa 6. A compound as in claim 1 where R is a secondary amyl group and R is -CH CN.

7. A compound as in claim 1 where R is a secondary amyl group and R is CI-I CH CN.

References Cited UNITED STATES PATENTS 3,120,554 2/1964 Baker et al. 260463 3,234,260 2/1966 Pianka et al 260463 FOREIGN PATENTS 1,217,384 5/1966 Germany 260463 LEWIS GOTTS, Primary Examiner D. G. RIVERS, Assistant Examiner US. Cl. X.R. 

